Production of diphenyl sulphones



Patented Oct. 2, 1945 rnopuc'rrou F DIPHENYL sum-norms j John Weiiiard, Westiield, and John Paul Messerly,

,Clarlr Township, Union County, Nrl -as'signors warm: a 0 Inc., Bahway, N. 1., a corporation of New Jerse v No Drawing.

are members oi the class conwhere R and R sisting of hydrogen, acylamino and nitrogroups; and is a member of the and groups, the oxidation being carried out in such manner, using an alkali hypohalogenite as the oxidizing agent, that oxidation dition of two or one oxygen atoms to; the central sulphide or sulphoxide radical. We have discovered that pecially sodium hypochlorite are particularly advantageousoxidizing agents for our purposes, resulting in quantitative yields of the desired 4,4- disubstituted-diphenyl sulphones. This represents a significant improvement over processes heretofore known for the production of the 4,4- disubstituted-diphenyl sulphones, oxidizing agents. such as hydrogen peroxide/have been utilized.

The products obtained according to our invention are useful in combating infections, or as intermediates for the production of such infectioncombating substances.

The following examples illustrate methods of carrying out the present invention, but it is to be understood that way of illustration, and not of limitation.

Example I oi crude 4,4'-di(acctylamino) -diphenyl sulphoxide are dissolved in 170 cc. of boiling'glacial acetic acid. 0.5 gm. of an activated carbon is added. The hot solution is filtered, and the carbon'residue is washed with cc. of'hot glacial acetic acid. 18 gms. of sodium hydroxide are dissolved in 200 cc. of water, 10.05 gms. of chlorine are dissolved in the solution-,--'and the solution is then made up to 250 cc. with water.

occurs by the adalkali hypohalogenites, and es-.

wherein other" processes I for prepar- Application February 4, 194$, Serial him-474,690; 1 i Y ja oisims. (em -tam); "t0 the" 'hOt (85) aceticacid solution of the oxidation is complete, as assulphoxide until the certained by the starch-potassium iodide test sothese examples are given by. I

The hypochlorite solution i added from a burette' lution using a spot plate. 1 7

400 cc; of water are added to the reaction mix- 'ture; thesolid is filtered off, and washed with water until free from hold, then dried at C.

a a M. P. of 288-289 c. i

8.5 gms. of the crude product are dissolved in 510cc. of hot %etha'nol. l'gm. or activated carbon is added, the mixture is filtered, 500 ;cc. of water are added-and the mixture is cooled to 5 'C. The crystals'are collectedona filter and'dried at 70 C. The product, 4,4-di(acetylamino) -diphenyl sulphone, has a melting point oi 291'- The product has Example [I timeters water is added. The mixture is subjected to fast stirring, the temperature being held at 4-8 0., for two hours. The mixture is then allowed to warm up to 20 C. and held there for /2 hour. The solid is filtered off, washed with water, and dried at 70 C.M. P. 230-240" C.

The crude product is triturated with cc. of hot methanol, cooled to 40. C., filtered, washed with methanol, and dried; the (acetylamino) -diphenyl:sulphone, has a melting point of 270-275 C. Onrecrystallization, as in Example I, the melting point 291-293 C. V

7 Example III 5.0 ms. 01 chlorine are dissolved in a solution of 5.6 g ns. sodium hydroxide in and the solution is made upto 100 cc. with water.

2 gms. of 4,4'-di-nitro-diphenyl sulphide are dissolved in 100 cc. of hot from a burette, with vigorous stirring. The mixture is held on the steam bath for 30 minutes.

diluted'with 200 cc. of water, cooled, filtered, and I The product, 4,4'-di-nitroe, melts at 285-290 C., with washed with water. diphenyl sulpho charting.

. Example IV UNI-Tao j STATES PA ENT l 10 gms. oi finely powdered diproduct, 4,4-dimay be raised to 75 cc. of water,

glacial acetic acid, and 20 cc. of the hypochlorite solution are added hypochlorite solution diiacylaniinm-dipheiiyl gsulphitie, r e V 1 amino) -dipheny1 sulphoxide, i,4!-1ilriitro-diphenyl. sulphideratid u' -amltm-qipnem suiphoxide.

' and recovering; the corresponding- 4,4 '-disubstitutedediphemrl sulphone. v; a V

r 3. The process that comprises reactinsan aquecus solution of alkali metal himhl qseniw-with I carrying out the was. V r 7 hot.vi:orously agiated; slacialaceticfacid sopresent invention, without departing from W Tspirit'and scopethereor, and we are to be-lirn ited only by the appended claims.

We claim:

1. The process that comprises a hot, yigorously ag'itated,jslaciai acetic acid sossulphoxide; and recovering "the gicorrespondins 4, '-d substit tedphenyl mlphone. 1 v2. The process that comprisesreactin'g an' aquemi solution of sodium hypochloritewith' a hot, vi or usl a d,"

glacial acetic acid solution the class consistins or,4.4'-

of 1 a 7 compound of 4,4'-Vdi(acyl- ,7 c an Mme? ous solution 0! alkali metal hypohalogenite with 4,4'-qiinitro' diphenyl' lution oi'a'compound oi the class eonsistinzotky- 4,4',-di(acy1amino)Y- diphenyl "sulphide, xii dit f (acylaminol-rdiphenyl sulphoxide, 4A -dinitro-V "diphenyi sulphide and lution of 4,4'-di(acylam1no)-diphenyl sulphide.

and recovering '4,4"- di(acylamino) v diphenyl sulphone. p 4.-Th e process 7 ousjsolution of sodiumhypochloritei'with a hot,

' 'vigorousiy agitated, glacialacetic acid, solution 1 of 4,4'-di(acylaminol-diphenyl sulphide; and recovering 4,4'-di(acylamino) -diphenyl sulphuric.

5. Th process that comprises reacting an aqueous solution 01' alkali metal hypohalogenite with a hot; vigorouslyagitated', glacial acetic acid soandirecoyering -4.4i"-di(acylarnino) -diphenyl Sui- 'vh n r i (j. r'li'h'e procs :ous soiution'o't sodium hypochlorite with abet,

vigorously agitatem'r'glacial acetic acid solution o'i".4,4'-di(acyiamino) -diphenyl sulphoxide, and

go.- recovering 4 ,4':-di'(a.cylamino) -diplieny 1 sulphcne.

; 7. :The process that cdmprisesreacting an agile- 'ous solution of, alkali metalfhirpohalolgenite with a but vigorously agitated, g'lacialf acetic f acid j solutionr'ot 4,4'-dinitro diphenyl sulphide, Midl fe?- g5 coveringlA' dinitro-dipheriyl'sulphone.

a0 7 flf-dinitro-diphenm sulphone.

' 8.- The process that comprises reacting an aqueous solution oi sodium hypochlorite with a hot, vigorously agitatedyglac'iai acetic acid. solution ox 4,4'-dinitrodiphenyl sulphide,v and recovering JOHN; wmamrip;

' JOHIN EAUI -MEB thatcomprises reactlng an aqua a thatcomprises mean: an aqua-- ERLY. r 

